The present invention relates to novel tetrazole derivatives, to processes for their preparation, to their intermediates, to their use as herbicides and to novel herbicidal compositions for use in paddy fields.
It has been already known that certain kinds of tetrazole derivatives show a herbicidal activity (cf. Japanese Laid-open Patent Application No. 12275/1999, No. 21280/1999 etc.). Furthermore, it has been known that certain kinds of heterocyclic derivatives show a herbicidal activity (cf. U.S. Pat. Nos. 5,834,402, 5,846,906, DE-A-19846792, WO 99/10327 etc.).
There have now been found novel tetrazole derivatives of the formula (I) 
wherein
R1 represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, C1-2 haloalkoxy, methylthio, ethylthio, C1-3 alkylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano,
R2 represents C1-6 alkyl or C3-6 cycloalkyl which may be optionally substituted with halogen or C1-3 alkyl, or represents C1-4 haloallyl, C2-6 alkenyl, or phenyl which may be optionally substituted with halogen, C1-3 alkyl, C1-2 haloalkyl or nitro,
m represents 0, 1 or 2,
and the two R1 substituents may be identical or different, in case m represents 2,
n represents 1 or 2,
Q represents one of the following groups 
wherein
R3, R4, R5, R6, R7 and R8 are identical or different and each represents a hydrogen atom or methyl,
R9 represents a hydrogen atom, halogen, C1-3 alkyl, halomethyl, methoxy or nitro,
R10 represents C1-6 alkyl,
R11 represents halogen, and
k represents 1 or 2.
The compounds of the formula (I), according to the invention, can be obtained by a process wherein
a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-1) or (Q-2):
compounds of the formula (II) 
wherein
R1, R2, m and n have the same definition as aforementioned, and
T1 represents one of the following groups 
wherein
R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,
are reacted to a rearrangement in the presence of inert solvents, and if appropriate, in the presence of a base and a cyanide, and if appropriate, in the presence of a phase-transfer catalyst,
or
b) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-6) or (Q-7) and R11 in said groups represents chloro or bromo:
compounds of the formula (Ib) 
wherein
R1, R2, m and n have the same definition as aforementioned, and
Qb represents one of the following groups 
wherein
R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,
are reacted with a halogenating agent in the presence of inert solvents,
or
c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-5):
compounds of the formula (Ic) 
wherein
R1, R2, m and n have the same definition as aforementioned, and
Qc represents one of the following groups 
wherein
R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,
R11c represents chloro or bromo,
are reacted with compounds of the formula (III)
R12xe2x80x94SHxe2x80x83xe2x80x83(III)
wherein
R12 represents the following group 
xe2x80x83or
R10 
wherein
R9, R10 and k have the same definition as aforementioned,
in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.
The tetrazole derivatives of the formula (I) provided by the present invention show stronger herbicidal activity than with the compounds described in the aforementioned prior art references.
In the formulae:
xe2x80x9cHalogenxe2x80x9d represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.
xe2x80x9cAlkylxe2x80x9d can be straight chain or branched chain and there can be specifically mentioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-, or tert-pentyl and n- or iso-hexyl.
xe2x80x9cCycloalkylxe2x80x9d includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. These cycloalkyls may be optionally substituted with halogen (for example, fluoro, chloro, bromo etc.), C1-3 alkyl (for example, methyl, ethyl, n- or iso-propyl etc.) and in case that a plurality of substituents exist, they may be identical or different. As specific examples of such substituted cycloalkyls there can be mentioned 1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-n-propylcyclopropyl, 1-methyl-2-fluorocyclopropyl, 2-methylcyclopropyl, 2-fluorocyclopropyl, 1-methyl-2,2-difluorocyclopropyl, 1-methyl-2,2-dichlorocyclopropyl, 2,2difluorocyclopropyl, 2-methylcyclopentyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl and 2,5-dimethylcyclohexyl.
As xe2x80x9calkenylxe2x80x9d there can be mentioned, for example, vinyl, allyl, 1-methylallyl, 1,1-dimetylallyl and 2-butenyl.
xe2x80x9cHaloalkylxe2x80x9d represents straight chain or branched chain alkyl, of which at least one hydrogen is substituted with halogen, and there can be mentioned, for example, C1-4 alkyl substituted with 1-6 fluoro and/or chloro, specifically difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, dichloromethyl, 2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl and 1,2,2,3,3,3-hexa-fluoropropyl.
The Haloalkyl part in xe2x80x9chaloalkoxyxe2x80x9d can have the same definition as the afore mentioned xe2x80x9chaloalkylxe2x80x9d and as xe2x80x9chaloalkoxyxe2x80x9d there can be specifically mentioned, for example, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2,2,2-trifluoroethoxy and 3-chloropropoxy.
xe2x80x9cAlkylsulfonylxe2x80x9d represents an alkyl-SO2-group, wherein the alkyl part has the above-mentioned meaning, and includes specifically methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl.
As preferred definitions in the formula (I) there can be mentioned:
R1 preferably represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, C1-2 haloalkoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano.
R2 preferably represents C1-3 alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, C1-3 haloalkyl, C2-4 alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro.
m preferably represents 1 or 2.
n preferably represents 1 or 2.
R9 preferably represents a hydrogen atom, fluoro, chloro, methyl, ethyl or tri-fluoromethyl.
R10 preferably represents methyl or ethyl.
R11 preferably represents chloro or bromo.
k preferably represents 1.
As more preferred definitions in the formula (I) there can be mentioned:
R1 more preferably represents chloro, bromo, methyl or methylsulfonyl,
R2 more preferably represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl,
m more preferably represents 2, and in this case the two R1 substituents are bond respectively to the 2-position and 4-position of a benzene ring and the two R1 substituents may be identical or different.
n more preferably represents represents 1.
In a most preferred group of the inventive compounds the group 
bonds to the 3-position (acccording to formula (I)) of the benzene ring. In another most preferred group Q represents one of the following groups 
The substituents among the different ranges of preference can be combined without limitation among each other. limitation among each other.
However, as a preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the preferred meaning as described above, and as a more preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the more preferred meaning as described above.
The aforementioned preparation process (a) can be illustrated by the following reaction formula, in case of using, for example, 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate as the starting material. 
The aforementioned preparation process (b) can be illustrated by the following reaction formula, in case of using, for example, 2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}cyclohexane-1,3-dione as the starting material, and, for example, oxalyl dichloride as chlorinating agent. 
The aforementioned preparation process (c) can be illustrated by the following reaction formula, in case of using, for example, 3-chloro-2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one and thiophenol as the starting materials. 
It is further mentioned that the group (Q-1) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms 
It is also mentioned that the group (Q-2) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms 
Thus, the compounds of the formula (I) of the present invention include the compounds of the formula (I) wherein Q represents the above-mentioned tautomeric groups (Q-1a), (Q-1b), (Q-2a) or (Q-2b) as group Q-1 or Q-2 respectively. In the present specification, however, it should be understood that these tautomeric groups are represented, unless specified, by the illustration of group (Q-1) or group (Q-2).
The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), are novel compounds which were not described in the literature up to the present and can be prepared according to the process described in various publications (e.g., Japanese Laid-open Patent Publications No. 222/1990, No. 173/1990, No. 6425/1990 etc.) by reacting compounds of the formula (IV) 
wherein
R1, R2, m and n have the same definition as aforementioned, and
M represents halogen,
with compounds of the formula (V)
Qaxe2x80x94Hxe2x80x83xe2x80x83(V)
wherein
Qa represents one of the following groups 
wherein
R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,
in an appropriate diluent, for example, dichloromethane, in the presence of an appropriate condensing agent, for example, triethylamine.
The compounds of the formula (IV) used in the above-mentioned reaction are also novel compounds which were not described in the literature up to the present and can be prepared, for example, by reacting compounds of the formula (VI) 
wherein
R1, R2, m and n have the same definition as aforementioned,
with a halogenating agent, for example, phosphorus oxychloride, phosphorusxe2x80x94oxy-bromide, phosphorus trichloride, phosphorus tribrornide, phosgene, oxalyl dichloride, thionyl chloride, thionyl bromide.
The compounds of the formula (V) used as the starting materials in the preparation of the compounds of the above-mentioned formula (II) are per se known and comrnercially available or can be easily prepared according to the processes described in various publications (e.g., Japanese Laid-open Patent Publications No. 6425/1990, No. 265415/1998, No. 265441/1998).
The compounds of the formula (VI) used for the preparation of the compounds of the above-mentioned formula (IV) are also novel compounds which were not described in the literature up to the present and can be easily prepared, for example, by hydrolyzing compounds of the formula (VI) 
wherein
R1, R2, m and n have the same definition as aforementioned, and
T2 represents C1-4 alkoxy, preferably methoxy or ethoxy,
in an appropriate diluent, for example, aqueous dioxane, in the presence of an appropriate base, for example, sodium hydroxide.
The compounds of the above-mentioned formula (VII) are also novel compounds and can be easily obtained, for example, by reacting compounds of the formula (VIII) 
wherein
R2 has the same definition as aforementioned
with compounds of the formula (IX) 
wherein
R1, m and n have the same defmition as aforementioned,
T2 represents C1-4 alkyl, preferably methyl or ethyl, and
M represents halogen,
in an appropriate diluent, for example, N,N-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.
The compounds of the above-mentioned formula (VIII) are known compounds described, for example, in Berichte Vol. 28, p. 74-76 (1895) and can be easily prepared according to the process described in said publication.
On the other hand, the compounds of the above-mentioned formula (IX), a part of which are novel compounds which were not described in the literature up to the present, can be easily prepared according to the process described, for example, in Japanese Laid-open Patent Publication No. 173/1990.
The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), can also be easily prepared from compounds of the aforementioned formula (VI) according to the process described, for example, in WO93/18031.
As typical examples of the compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a), the followings can be mentioned:
3-Oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 2-{[(1-cyclopropyl-1Htetrazol-5-yl)thio]methyl}-4-fluorobenzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,
3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 4-bromo-2-{[(1-phenyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluorometh-ylbenzoate,
3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylbenzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]meth-yl}benzoate,
3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-(2-chlorophenyl)-1H-tetrazol-5-yl)thio]-methyl}benzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(n-pentyl)-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(3-difiuoromethylphenyl)-1H-tetrazol-5-yl)-thio]methyl}-4-methylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfanylbenzoate,
3-oxo-1-cyclohexenyl 2,4-dimethylsulfanyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,
3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfonylbenzoate,
3-oxo-1-cyclohexenyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methoxybenzo-ate,
3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methylsulfon-yloxybenzoate,
3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,
3-oxo-1-cyclohexenyl 4-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,
5,5-dimethyl-3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoate,
4,4-dimethyl-3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,
4,4-dimethyl-3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)-thio]methyl}benzoate,
4-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyloxy}-bicyclo[3.2.1]-3ecten-2-one,
4-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyloxy}bi-cyclo[3 .2.1]-3-octen-2-one,
4-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyloxy}bicyclo[3.2.1]-3-octen-2-one.
As typical examples of the compounds of the formula (IV) used as the starting materials in the preparation of the compounds of the aforementioned formula (II), the followings can be mentioned:
4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl chloride,
2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl chloride,
2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl chloride,
2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,
4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoyl chloride,
2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl bromide,
2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl bromide,
2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl bromide.
As typical examples of the compounds of the formula (VI) used as the starting materials in the preparation of the compounds of the aforementioned formula (IV), the followings can be mentioned:
4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoic acid,
2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
2-chloro-3-{[(1-methyl-1Htetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoic acid,
2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoic acid,
2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,
4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoic acid.
As typical examples of the compounds of the formula (VII) used as the starting materials in the preparation of the compounds of the aforementioned formula (VI), the followings can be mentioned.
Methyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
methyl 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,
methyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoate,
methyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,
methyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,
methyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,
methyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate,
methyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
methyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
methyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoate,
ethyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,
ethyl 2-chloro-3-{[(1-methyl-1H-tetrarol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,
ethyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate.
The compounds of the formula (Ib), starting materials in the aforementioned preparation process (b), are a part of the compounds of the formula (a) of the present invention and can be easily prepared according to the above-mentioned preparation
process (a).
As typical examples of the compounds of the formula (Ib) used as the starting materials in the aforementioned preparation process (b), the followings, included in the formula (I), can be mentioned:
2-{4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,
2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,
2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoyl}cyclo-hexane-1,3-dione,
2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,
2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}cyclo-hexane-1,3-dione,
2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}cyclohexane-1,3-dione,
2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}cyclohexane-1,3-dione,
2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,
2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,
2-{4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoyl}-cyclohexane-1,3-dione,
3-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}bicyclo[3.2.1]-octane-2,4-dione
As a halogenating agent used for the reaction with the compounds of the formula (Ib) in the preparation process (b) there can be mentioned, for example, thionyl chloride, thionyl bromide, oxalyl dichloride, oxalyl dibromide etc.
The compounds of the formula (Ic), the starting materials in the aforementioned preparation process (c), are a part of the compounds of the formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process (b).
As typical examples of the compounds of the formula (Ic) used as the starting materials in the aforementioned preparation process (c), the followings, included in the formula (I), can be mentioned:
3-Chloro-2-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}-2-cyclohexen-1-one,
3-chloro-2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-hexen-1-one,
3-chloro-2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,
3-chloro-2-{4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoyl}-2-cyclohexen-1-one,
4-chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}4-methyl-sulfonylbenzoyl}bicyclo[3.2.1]-3-octen-2-one.
The compounds of the formula (III), the starting materials in the above-mentioned preparation process (c), are thiol compounds well known in the field of organic chemistry and as typical examples of the compounds of the formula (III) the followings can be mentioned:
Methyl mercaptan,
ethyl mercaptan,
thiophenol,
4-fluorothiophenol,
4-chlorothiophenol,
2-methylthiophenol,
4-ethylthiophenol,
4-triflubromethylthiophenol etc.
Each compound of the formulae (II), (V), (VI) and (VII), starting material or intermediate product in the aforementioned processes (a)-(c) for the preparation of the compounds of the formula (I) of the present invention is a novel compound which was not described in the literature up to the present. The compounds can be illustrated collectively by the following general formula (X) 
wherein
W represents T1, hydroxy or T2, wherein
R1, R2, m, n, T1, T2 and M have the same definition as aforementioned.
The reaction of the aforementioned preparation process (a) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, toluene, dichloromethane, chloroform and 1,2-dichloroethane; ethers, for example, ethyl ether, dimethoxyethane (DME) and tetrahydrofuran (THF); ketones, for example, methyl isobutyl ketone (MIBK); nitrites, for example, acetonitrile; esters, for example, ethyl acetate; acid amides, for example, dimethylformamide (DMF).
The preparation process (a) can be conducted in the presence of a cyanide and a base. As a cyanide usable in that case there can be mentioned, for example, sodium cyanide, potassium cyanide, acetone cyanohydrin and hydrogen cyanide. As a base there can be mentioned, for example, as inorganic bases, hydroxides and carbonates of alkali metals and alkaline earth metals, for example, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).
The aforementioned preparation process (a) can be conducted also in the co-existence of a phase-transfer catalyst. As examples of the phase-transfer catalyst usable in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, 18-crown-6 and 15-crown-5.
The reaction of the preparation process (a) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9210 to about 80xc2x0 C., preferably about 5 to about 40xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process (a) the target compounds of the afore mentioned formula (I), in case that Q represents groups (Q-1) or (Q-2), can be obtained, for example, by reacting 1 mole of a compound of the formula (II) with 1 to 4 moles of triethylamine in a dildent, for example, acetonitrile, in the presence of 0.01 to 0.5 moles of acetone cyanohydrin.
In conducting the preparation process (a) it is possible to obtain the compounds of the formula (I) by conducting reactions starting from the compounds of the aforementioned formula (VI) continuously in one pot without isolating the compounds of the formulae (IV) and (II).
The reaction of the aforementioned preparation process (b) can be conducted in an appropriate diluent. As examples of such there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chloro-benzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MEBK); nitrites, for example, acetonitrile and propionitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and hexamethyl-phosphoric triamide (HMPA).
The reaction of the preparation process (b) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9220 to about 100xc2x0C., preferably about 0 to about 50xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process (b) the target compounds of the afore mentioned formula (I), in case that Q represents groups (Q-6) or (Q-7), wherein R11 in said group represents chloro or bromo, can be obtained, for example, by reacting 1 mole of a compound of the formula (Ib) with 1 to 5 moles of oxalyl dichloride in a diluent, for example, dichloromethane.
The reaction of the aforementioned preparation process (c) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile and acrylonitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethyl-formamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone; sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) and sulfolane; bases, for example, pyridine.
The preparation process (c) can be conducted in the presence of a condensing agent. As a usable condensing agent there can be for example mentioned, as inorganic bases, hydrides and carbonates of alkali metals, for example, sodium hydride, lithium hydride, sodium carbonate and potassium carbonate; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediarnine (TMEDA), pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-iazabicyclo[5,4,0]undec-7-ene (DBU).
The reaction of the preparation process (c) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about xe2x88x9220 to about 140xc2x0 C., preferably about 0 to about 100xc2x0 C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.
In conducting the preparation process (c) the target compounds of the afore-mentioned formula (I), in case that Q represents groups (Q-3), (Q-4) or (Q-5) can be obtained, for example, by reacting 1 mole of a compound of the formula (Ic) with 1 to 5 moles of thiophenol in a diluent, for example, tetrahydrofuran in the presence of 1 to 5 moles of triethylamine.
The active compounds of the aforementioned formula (I), according to the present invention, show, as shown in the biological test examples to be described later, excellent herbicidal activities against various weeds and can be used as herbicides. In the present specification weeds mean, in the broadest sense, all plants which grow in locations where they are undesired. The compounds, according to the present invention, act as total or selective herbicides depending upon the applied concentration. The active compounds, according to the present invention, can be used, for example, between the following weeds and cultures.
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Cheno-podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia etc.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon etc.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.
The use of the compounds, according to the present invention, is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner. The active compounds, according to the present invention, can, depending upon the applied concentration, non-selectively control weeds and can be used, for example, on industrial terrain, rail tracks, paths, places with or without tree plantings. Moreover, the active compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, for example, afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hopfields etc. and can be applied also for the selective controlling of weeds in annual cultures.
According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional breeding and optimizing processes or by biotechnological and genetic engineering methods or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plant parts also includes harvested crops and propagation material, e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds.
According to the invention the plants and plant parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting, fogging, spreading and in the case of propagation material also by coating using one or multiple layers.
The active compounds, according to the present invention, can be made into the customary formulations. As such formulations there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water-dispersible granules, tablets, granules, suspension-emulsion concentrates, microcapsules in polymeric substances, jumbo formulations etc.
These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydro-carbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycol etc.) and their ethers, esters etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulphoxide etc.) and water. In case of using water as extender, for example, organic solvents can be used as auxiliary solvents.
As solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. As solid carriers for granules there can be mentioned, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.), synthetic granules of inorganic and organic meals, particles of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks etc.) etc.
As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates etc.)], albumin hydrolysis products etc.
Dispersants include, for example, ligninsulphite waste liquor, methyl cellulose etc.
Tackifiers can also be used in formulations (powders, granules, emulsions). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc.).
Colorants can also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc.) and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc.
Said formulations can contain the active compounds of the formula (I) in a range of generally 0.1 to 95 % by weight, preferably 0.5 to 90 % by weight.
The active compounds of the formula (I), according to the present invention, can be used as such or in their formulation forms for controlling weeds. They can be used also as a mixed agent with known herbicides. Such a mixed agent can be previously prepared as a final formulation form or can be prepared by tank-mixing on occasion of application. As herbicides usable in combination with the compounds of the formula (I), according to the present invention, as a mixed agent there can be specifically mentioned, for example, the following herbicides shown in common names.
Acetamnide type herbicides, for example, pretilachlor, butachlor, tenylchlor, alachlor etc.;
amide type herbicides, for example, clomeprop, etobenzanid etc.;
benzofuran type herbicides, for example, benfuresate etc.;
indanedione type herbicides, for example, indanofan etc.;
pyrazole type herbicides, for example, pyrazolate, benzofenap, pyrazoxyfen etc.;
oxazinone type herbicides, for example, oxaziclomefone etc.;
sulfonylurea type herbicides, for example, bensulfuron-methyl, azimsulfuron,
imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamron Ethoxysulfuron, Halosulfuiron (-methyl) etc.;
thiocarbamate type herbicides, for example, thiobencarb, molinate, pyributycarb etc.;
triazine type herbicides, for example, dimethametryn Simetryn etc.;
triazole type herbicides, for example, cafenstrole etc.;
quinoline type herbicides, for example, quinclorac etc.;
isoxazole type herbicides, for example, isoxaflutole etc.;
dithiophosphate type herbicides, for example, anilofos etc.;
oxyacetamide type herbicides, for example, mefenacet, flufenacet etc.;
tetrazolinone type herbicides, for example, fentrazamide etc.;
dicarboxyimide type herbicides, for example, pentoxazone etc.;
trione type herbicides, for example, sulcotrione, benzobicyclon etc.;
phenoxypropinate type herbicides, for example, cyhalofop-butyl etc.;
benzoic acid type herbicides, for example, pyriminobac-methyl etc.;
diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;
pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;
phenoxy type herbicides, for example, MCPA, MCPB etc.;
urea type herbicides, for example, dymron, cumyluron etc.;
naphthalenedione type herbicides, for example, quinoclamine etc.;
isoxazolidinone type herbicides, for example, clomazone etc.
diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;
pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;
phenoxy type herbicides, for example, MCPA, MCPB etc.;
urea type herbicides, for example, dymron, cumyluron etc.;
naphthalenedione type herbicides, for example, quinoclamine etc.;
isoxazolidinone type herbicides, for example, clomazone etc.
In addition to the above mentioned herbicides, the following herbicides, shown in common names, for example, Acetochlor, Acifluorfen (-sodium), Aclonifen, Alloxydirn (-sodium), Ainetryne, Amicarbazone, Amidochlor, Amidosulfuron, Arnitrole, Asulam, Atrazine, Azafenidin, Beflubutamid, Benazolin (-ethyl), Bentazon, Benzfendizone, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac -(sodium), Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butafenacil -(allyl), Butenachlor, Butralin, Butroxydim, Butylate, Carbetamide, Carfentrazone (-ethyl), Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlorthiarnid, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosuffiron, Clefoxydim, Clethodim, Clodinafop (-propargyl), Clopyralid, Cloransulam (-methyl), Cyanazine, Cybutryne, Cycloate, Cycloxydim, 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlobenil, Dichlorprop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenopenten (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dikegulac (-sodium), Dimefuron, Dimepiperate, Dimethachlor, Dimethenamid (-P), Dimexyflam, Dinitramine, Diphenamid, Diquat (-dibromide), Diuron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethiozin, Ethofumesate, Ethoxyfen, Fenoxaprop (-P-ethyl), Flamprop (-M-isopropyl, -M-methyl), Flazasuilron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Fluchloralin, Flumetsulam, Flumiclorac (-pentyl), Flumiox-azin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fomesafen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-ammonium, -isopropylammonium), Halosafen, Haloxyfop (-ethoxy-ethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imaza-mox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Iodosulfuron (-methyl, -sodium), Ioxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxadifen (-ethyl), Isoxapyrifop, Ketospiradox, Lactofen, Lenacil, Linuron, Mecoprop (-P), Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Methyldymron, Metobenzuron, Metobromuron, (S-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfliron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Paraquat, Pelargonsaure, Pendimethalin, Pendralin, Pethoxamid, Phenmedipham, Picolinafen, Piperophos, Primisulfuiron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazogyl, Pyribenzoxim, Pyridafol, Pyridate, Pyridatol, Pyriftalid, Pyrithiobac (-sodium), Quinmerac, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfiron, Sethoxydim, Simazine, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thiazopyr, Thidiazimin, Thifensuifiron (-methyl), Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tnidiphane, Trifloxy-sulfuron, Trifluralin, Triflusuulfuron (-methyl), Tritosulfiuron.
The above-mentioned herbicides are known herbicides mentioned in xe2x80x9cPesticide Manualxe2x80x9d 2000, published by The British Crop Protect Council.
The weight ratios of the groups of active substances in the mixed compositions can vary within relatively wide ranges.
For instance, per part by weight of (1) the compounds of the formula (I),
0.2 to 14 parts by weight of acetamide type herbicides, preferably 0.66 to 5 parts by weight;
2 to 40 parts by weight of amide type herbicides, preferably 3.96 to 16 parts by weight;
0.2 to 20 parts by weight of benzofuran type herbicides, preferably 1.00 to 6 parts by weight;
0.2 to 8 parts by weight of indanedione type herbicides, preferably 0.49 to 2 parts by weight;
0.06 to 4 parts by weight of oxazinone type herbicides, preferably 0.20 to 0.8 parts by weight;
0.02 to 4 parts by weight of sulfonylurea type herbicides, preferably 0.07 to 1.2 parts by weight;
1 to 100 parts by weight of thiocarbamate type herbicides, preferably 2.47 to 40 parts by weight;
0.6 to 12 parts by weight of triazine type herbicides, preferably 1.32 to 4.5 parts by weight;
0.1 to 8 parts by weight of triazole type herbicides, preferably 0.33 to 3 parts by weight;
0.2 to 10 parts by weight of dithiophosphate type herbicides, preferably 1.00 to 4 parts by weight;
0.2 to 50 parts by weight of oxyacetamide type herbicides, preferably 1.00 to 12 parts by weight;
0.02 to 10 parts by weight of tetrazolinone type herbicides, preferably 0.17 to 3 parts by weight;
0.1 to 12 parts by weight of dicarboxyimide type herbicides, preferably 0.33 to 4.5 parts by weight;
0.2 to 12 parts by weight of phenoxypropinate type herbicides, preferably 0.4 to 1.8 parts by weight;
0.6 to 20 parts by weight of diphenylether type herbicides, preferably 1.65 to 7.5 parts by weight;
0.02 to 14 parts by weight of pyridinedicarbotlioate type herbicides, preferably 0.20 to 5 parts by weight;
0.2 to 10 parts by weight of phenoxy type herbicides, preferably 0.66 to 4 parts by weight, and
2 to 80 parts by weight of urea type herbicides, preferably 4.95 to 25 parts by weight,
are used.
Furthermore, the active compounds of the formula (I) according to the present invention, can be mixed also with a safener and their application as a selective herbicide can be broadened to reduce phytotoxicity and to provide wider weed-control spectrur by such a mixing.
As an example of the safener, the following safeners can be mentioned; AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG-191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.
The above-mentioned safeners are known safeners mentioned in xe2x80x9cPesticide Manualxe2x80x9d, 2000, published by The British Crop Protect Council.
The weight ratios of the groups of active substances in the mixed comositions can vary within relatively wide ranges.
For instance, per part by weight of (1) the compounds of the formula (I),
0.05 to 50 parts by weight of Dichlormid, preferably 0.1 to 10 parts by weight;
0.05 to 50 parts by weight of Dymron, preferably 0.1 to 10 parts by weight;
0.05 to 50 parts by weight of Fenclorim, preferably 0.1 to 10 parts by weight;
0.05 to 50 parts by weight of Mefenpyr (-diethyl), preferably 0.1 to 10 parts by weight; and
0.05 to 50 parts by weight of Naphthalic anhydride, preferably 0.1 to 10 parts by weight, are used.
And furthermore, the above-mentioned combinations of the compounds of the. formula (I), according to the present invention, and the above-mentioned herbicides can be mixed with also the above-mentioned safeners and their application as selective herbicidal compositions can be broadened to reduce phytotoxicity and to provide wider weedxe2x80x94control spectrum by mixing safeners and/or other selective herbicides.
Surprisingly, some of the mixed compositions, according to the present invention show synergistic effects.
In case of using the active compounds of the formula (I) and their mixed compositions, according to the present invention, they can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsions, tablets, suspensions, powders, pastes, granules or used in the use forms prepared by further dilution. The active compounds of the present invention can be applied by means of, for example, watering, spraying, atomizing, granule application etc.
The active compounds of the formula (I) and their mixed compositions, according to the present invention, can be used at any stages before and after germination of plants. They can also be taken into the soil before sowing.
The application amount of the active compounds of the formula (I) and their mixed compositions, according to the present invention, can be varied in a substantial range and are fundamentally different according to the nature of the desired effect. In case of using as herbicides, as the application amount there can be mentioned, for example, ranges of about 0.01 to about 3 kg, preferably about 0.05 to about 1 kg of the active compounds per hectare.